CN102365179A - Hard coating composition, multi-layered sheet using the same, and preparation method thereof - Google Patents
Hard coating composition, multi-layered sheet using the same, and preparation method thereof Download PDFInfo
- Publication number
- CN102365179A CN102365179A CN2009801583480A CN200980158348A CN102365179A CN 102365179 A CN102365179 A CN 102365179A CN 2009801583480 A CN2009801583480 A CN 2009801583480A CN 200980158348 A CN200980158348 A CN 200980158348A CN 102365179 A CN102365179 A CN 102365179A
- Authority
- CN
- China
- Prior art keywords
- coating composition
- hard coating
- layer
- composite wafer
- adhesive linkage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
- B44C3/02—Superimposing layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a general shape other than plane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/406—Bright, glossy, shiny surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2419/00—Buildings or parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2451/00—Decorative or ornamental articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2479/00—Furniture
Abstract
The hard coating composition of the present invention comprises about 5-60 wt% of fluorinated acrylate compounds, about 5-50 wt% of a (metha) acrylate monomer, about 0.1-10 wt% of a photopolymerization initiator, and about 1-35 wt% of a bisphenol-based resin. The hard coating composition has a low failure rate and a high smoothness of coated surface, and can show an excellent texture of high gloss.
Description
Technical field
The present invention relates to hard coating composition, comprise the composite wafer of this hard coating composition, with and preparation method thereof.More specifically, the present invention relates to such hard coating composition, it comprises the bisphenols resin, the coating surface of low ratio of defects and high-flatness can be provided, and can show excellent gloss quality.Further, the present invention relates to be used to decorate the composite wafer that comprises hard coating composition of high glaze curved surface, and preparation method thereof.
Background technology
Decorative panel is used to decorate the surface such as products such as electrical equipment, furniture, inner wall of building or exterior walls.Decorative panel generally comprises the decorative layer with printed patterns and overlays the glass flake on the decorative layer.
When being certain preparation of product decorative panel, the glass flake by this product size cutting decorative panel forms decorative layer then on this glass flake.Here, the method that forms decorative layer comprise direct with printing ink the direct print process of printed patterns on the glass flake, through transfer paper with pattern heat transfer to thermal shift assay on the glass flake, the decorating film that will have a printed patterns is adhered to bonding method on the glass flake etc.
Yet, in these conventional methods, must form decorative layer to close to tie up on the corresponding glass flake one to one, this makes continued operation be difficult to execution and makes process complicacy and manufacturing cost height.
Recently, such as the metal outer material of electrical equipments such as refrigerator, washing machine by replacements such as plastic material such as ABS.Yet, comprise that the conventional decorative panel of this kind glass flake is inappropriate for decoration plastic outer material.
Particularly because the thermal coefficient of expansion of plastic material is about 10 times of glass, so between this decorative panel and the plastic material because shrinkage factor difference that variations in temperature produced is serious.Therefore; When the decorative panel that comprises glass flake is attached to the product of being processed by plastic material and is exposed to repeatedly the hot environment that changes and low temperature environment following time, this decorative panel often owing to its with the plastic outer material between shrinkage factor difference and separate with this exterior material.Especially, this kind phenomenon shows very seriously in the thermal cycle test of estimating the electrical equipment durability, and makes electrical equipment break down.
In order to solve this kind problem, attempted to replace the glass flake of decorative panel with plastic material.Yet, because the impact strength of plastic material and resistance to marring are less than glass and might be by being made dirty, so plastic material is not suitable for being used as the exterior material of decorative panel.
In order to address this problem; The glass flake of decorative panel is replaced with plastic tab; And thereby the formation hard conating is developed the decorative panel that makes new advances on this plastic tab, and this decorative panel is excellent in the physical property of aspects such as resistance to impact, resistance to marring, pencil hardness (pencil hardness), antifouling property.
Yet when forming hard conating for the moulded work that behind vacuum mo(u)lding, has curved surface, roller coat can't form hard conating, and flow coat is poor for the coating performance of hard conating.In addition, when forming hard conating on the original sheet of the product that has curved surface in advance, have such problem: the rounded portions office of this product might form crackle in moulding process.Therefore, when moulding has the product of curved surface, after forming the former thin slice that is not applied, obtain hard conating through spraying or dip-coating.Yet this process cost is high and coating surface that provided is lower than the flatness of plane hard conating, thereby makes the gloss deterioration of coating.Though developed the spary coating type coating with improved flow leveling, their cost is also high and owing to the restriction (limits) of spary coating type coating has high ratio of defects.In some cases, insert film and be used to decorate, but have limited range of application, for example only be applied to injection moulded products.And, insert the film resistance to marring low and also therefore be difficult to be applied in the vacuum mo(u)lding technology because of undercapacity has.
Summary of the invention
[technical problem]
The present invention relates to show the hard coating composition of excellent surface hardness and molding processability ability.
The invention still further relates to the hard coating composition that has low ratio of defects and can demonstrate the high glaze quality.
The invention still further relates to the hard coating composition that shows outstanding adhesion.
The invention still further relates to the hard coating composition that shows excellent transmittance and glossiness.
The invention still further relates to the hard coating composition that can be applied on the crooked decorative panel.
The invention still further relates to and comprise this hard coating composition and show excellent surface hardness and the composite wafer of molding processability ability.
The invention still further relates to and utilize this hard coating composition to come easily to make the method for this composite wafer.
[technical scheme]
One aspect of the present invention provides hard coating composition.This hard coating composition can comprise the bisphenols resin of about 5 to 60wt% fluorate acrylic acid ester compounds, (methyl) acrylate monomer of about 5 to 50wt%, about Photoepolymerizationinitiater initiater of 0.1 to 10wt% and about 1 to 35wt%.
This hard coating composition may further include about light stabilizer of 0.01 to 1wt%.
The viscosity of this hard coating composition under 25 ℃ can be for about 1 to about 300cps.
This hard coating composition may further include about solvent of 5 to 80wt%.
Another aspect of the present invention provides the composite wafer that comprises this hard coating composition.This composite wafer can comprise the hard conating of being made up of this hard coating composition; With the plastic tab layer that is formed on this hard conating one side.
Can with this hard conating be deposited on this plastic tab layer to thickness be about more than 1 to less than about 12.
This hard conating can when 200% percentage elongation molded (moulding), do not have crackle, and case hardness can be for more than the 4H for about more than 95% based on the glossiness of ASTM D-2457.
This plastic tab can be formed with decorating film on opposite side.This composite wafer can have the shape that comprises curved surface.
This decorating film can comprise the print film that is formed on the substrate layer.
This decorating film may further include the pressure-sensitive adhesive layer on this printed layers.
This decorating film can comprise first hyaline membrane, be formed on first adhesive linkage on this first hyaline membrane, be attached to this first adhesive linkage substrate layer, be formed on printed layers on this substrate layer, be formed on second adhesive linkage on this printed layers, be attached to second hyaline membrane of this second adhesive linkage and be formed on the pressure-sensitive adhesive layer on this second hyaline membrane.
In this substrate layer, printed layers, second adhesive linkage and second hyaline membrane at least one can have convex and concave patterns.
Other aspects of the present invention provide the method for making composite wafer.This method comprises and a) prepares flat compound foil that it comprises decorating film and is formed on the plastic tab layer on this decorating film one side; B) will be deposited on this plastic tab layer according to each described hard coating composition in the claim 1 to 4; C) through form the hard conating of precuring with this hard coating composition of UV light irradiation; The flat compound foil that d) will have a precuring hard conating is molded as the have curved surface net shape on (surface); And e) solidifies hard conating through form main (main) with this precuring hard conating of UV light irradiation.
In step c), this UV light can be according to about 200 to 300mJ/cm
2UV dosage irradiation.The case hardness of this precuring hard conating can be about 1B to 1H.
In step e), this UV light can be according to 500mJ/cm
2Above UV dosage irradiation.This main case hardness of solidifying hard conating can be for more than the 4H.
This hard coating composition can be deposited into thickness on this plastic tab layer be extremely less than 12 more than 1.
This decorating film can form through following steps: thus form second adhesive linkage on this printed layers forming printed layers on the substrate layer and adhesive is applied to; Second hyaline membrane is arranged on this second adhesive linkage and makes this substrate layer, printed layers, second adhesive linkage and thereby second hyaline membrane combines the preparation single sheet; Utilize embossing calender on this thin slice, to form relief pattern; Thereby adhesive is applied on this first hyaline membrane forms first adhesive linkage; The thin slice that will have a relief pattern be arranged on this first adhesive linkage in case this substrate level to this first adhesive linkage, thereby and the thin slice that makes this first hyaline membrane, first adhesive linkage and be formed with relief pattern on it combine to prepare preparatory decorating film; And with pressure-sensitive adhesive be applied to this preparatory decorating film (pre-decorative film) thus second hyaline membrane on form pressure-sensitive adhesive layer.
[beneficial effect]
According to embodiment of the present invention, comprise that the composite wafer of hard coating composition can have the coating surface of low ratio of defects and high-flatness (smoothness), and can show excellent high glaze quality.In addition, the superior physical properties of this composite wafer aspect impact strength, resistance to marring, hardness, antifouling property, and have extensive use.
Description of drawings
Fig. 1 is a flow chart of making the method for crooked composite wafer according to embodiment of the present invention.
Fig. 2 is a schematic flow sheet of making the method for crooked composite wafer according to embodiment of the present invention.
Fig. 3 illustrates an embodiment who makes the method for crooked composite wafer according to embodiment of the present invention.
Fig. 4 illustrates the decorating film according to one embodiment of the present invention.
Fig. 5 illustrates the decorating film according to another embodiment of the present invention.
Fig. 6 illustrates the decorating film of other embodiments according to the present invention.
The specific embodiment
Hard coating composition
Hard coating composition according to embodiment of the present invention comprises fluorate acrylic acid ester compounds, (methyl) acrylate monomer, Photoepolymerizationinitiater initiater and bisphenols resin.
In one embodiment, this fluorate acrylic acid ester compounds can be a copolymer, and the substituting group of the compound of wherein fluoridizing such as fluorine-based and fluoroalkyl are attached on the acrylate main chain with 3 above functional groups.In one embodiment, this fluorate acrylic acid ester compounds copolymer that is polyfunctional acrylic ester monomer and fluorate acrylic acid ester compounds.In another embodiment, fluorinated acrylic monomers, oligomer or homopolymers also can be suitable as the fluorate acrylic acid ester compounds.
This acrylate compounds of fluoridizing can be represented with formula I:
Wherein each among X1, X2 and the X3 is hydrogen or fluorine; Y1 is straight or branched fluoroalkane, ring-type fluoroalkane, straight or branched fluoroalkane hydroxide; And n is about integer of 1 to 10,000.
For example, this fluorate acrylic acid ester compounds is D-201MC (obtaining from DaiNippon Ink Chemicals), but is not limited to this.
This hard coating composition preferably includes about 5 to about 60wt% fluorate acrylic acid ester compounds, and more preferably from about 10 to about 50wt%, also 15 to about 45wt% fluorate acrylic acid ester compounds more preferably from about.When the amount of this fluorate acrylic acid ester compounds is less than 5wt%, the antifouling property that said composition can't obtain to expect, and when the amount of this fluorate acrylic acid ester compounds surpassed 60wt%, the resistance to marring of said composition and wearability may deteriorations.
Should (methyl) acrylate monomer can be (methyl) acrylate monomer that does not contain the annular aliphatic structure.Should can be selected from simple function (methyl) acrylate monomer, difunctionality (methyl) acrylate monomer, trifunctional (methyl) acrylate monomer or more multi-functional (methyl) acrylate monomer by (methyl) acrylate monomer, and composition thereof.
The instance of simple function (methyl) acrylate monomer includes, but are not limited to, butyl acrylate, (methyl) allyl acrylate, acrylic acid 2-methoxyl group ethyl ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy methyl etc.
The instance of difunctionality (methyl) acrylate monomer includes, but are not limited to, and 1,6-hexanediyl ester (HDDA), 1,3-butanediol two (methyl) acrylic acid ester (BGDMA), tripropylene glycol diacrylate (TPGDA) etc.
The instance of trifunctional (methyl) acrylate monomer or more multi-functional (methyl) acrylate monomer comprises; But be not limited to; Trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), and double pentaerythritol methacrylate (DPHA) etc.
This hard coating composition can further comprise as required fluoridizes (methyl) acrylate monomer, carbamate (methyl) acrylic acid ester (urethane (meth) acrylate) monomer or oligomer etc., so that control the viscosity of said composition or so that strengthen its antifouling property.
This hard coating composition preferably includes (methyl) acrylate monomer of about 5 to about 50wt%, more preferably comprises (methyl) acrylate monomer of about 5 to about 40wt%, also more preferably comprises (methyl) acrylate monomer of about 7 to about 35wt%.If the amount of this (methyl) acrylate monomer is less than about 5wt%, then this hard conating can have low hardness, and if the amount of this (methyl) acrylate monomer surpasses about 50wt%, the desirably too much increase of the hardness of this hard conating.
Term " hardness of hard conating " is meant the state of this hard conating after final solidification process,, stands regelate process (secondary curing process) that is, that is, and and the hardness of the main cured layer of the main solidification process in the step e).
When with UV light irradiation, this Photoepolymerizationinitiater initiater produces free radical, the catalytic crosslinking reaction again of this free radical.This Photoepolymerizationinitiater initiater can be selected from any Photoepolymerizationinitiater initiater that is used for the curable composition of general UV-.The instance of Photoepolymerizationinitiater initiater comprises; But be not limited to; Benzophenone comprises 1-hydroxy-cyclohexyl phenyl ketone (Irgacure-184), α, the blend of alpha, alpha-dimethyl oxygen base-Alpha-hydroxy acetophenone (Darocure 1173) and 1-hydroxyl-cyclohexyl-phenyl ketone and benzophenone; And 2-hydroxy-2-methyl-1-phenyl-propane.
Said composition can comprise the Photoepolymerizationinitiater initiater of about amount of 0.1% to 10wt%.If the amount of this Photoepolymerizationinitiater initiater is less than about 0.1wt%, then this hard conating may solidify insufficient, and if the amount of this Photoepolymerizationinitiater initiater surpasses about 10wt%, then some Photoepolymerizationinitiater initiaters will be residual as impurity, this can reduce the hardness of this hard conating.This hard coating composition preferably includes about Photoepolymerizationinitiater initiater of 0.5 to 5wt%, more preferably comprises about Photoepolymerizationinitiater initiater of 0.7 to 3wt%.
According to the present invention, this hard coating composition comprises the bisphenols resin that is used to clean and remove the coating stain.Particularly, this hard coating composition can comprise that refractive index is about bisphenols resin more than 1.50.In one embodiment, the scope of the resinoid refractive index of this bis-phenol is about 1.50 to 3.00.For example, the diacrylate resin of this bisphenols resin bisphenol-A that is the oxirane modification.
This hard coating composition can comprise about 1 to 35wt% bisphenols resin.If the resinoid amount of this bis-phenol is less than about 1wt%, then this bisphenols resin is not remarkable to the effect that said composition produces, and if the resinoid amount of this bis-phenol surpasses about 35wt%, then this hard conating has low case hardness.Said composition can comprise about 3 to 20wt% bisphenols resin, preferred about 5 to 15wt% bisphenols resin.
According to the present invention, consider coating performance, the rate of drying (drying rate) of product, and outward appearance or productive rate, this hard coating composition may further include organic solvent.
The instance of organic solvent can comprise; But be not limited to; Methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, butanols, isobutanol, ethyl cellosolve, methyl cellosolve, butyl cellosolve, butyl acetate, ethyl acetate, diacetone alcohol, MEK, propane diols isopropyl alcohol (propyleneglycol isopropyl alcohol), ethylene glycol, isopropyl alcohol, and composition thereof.Can these organic solvents be used separately or be used in combination its two or more.The preferred mixture that uses about 3 to the 5 kinds of solvents that are selected from these organic solvents.
Said composition preferably includes about organic solvent of 5 to about 80wt%.If the amount of this organic solvent is less than about 5wt%; Then the deterioration owing to the said composition coating performance makes this hard coating composition can't form uniform films; If the amount of this organic solvent surpasses about 80wt%; Then this coated film becomes too thin, causes antifouling property, resistance to marring and wearability deterioration thus.In one embodiment, said composition comprises about organic solvent of 10 to about 70wt%.In another embodiment, said composition comprises about organic solvent of 30 to about 60wt%.
This hard coating composition may further include light stabilizer.This light stabilizer can strengthen the photostability of this hard conating, thereby prevents that this hard conating performance from changing along with the time.
This light stabilizer can suitably be selected according to the kind of used Photoepolymerizationinitiater initiater.For example, if this Photoepolymerizationinitiater initiater is benzophenone material such as α, alpha, alpha-dimethyl oxygen base-Alpha-hydroxy acetophenone (Darocure 1173) etc.; Then light stabilizer can be selected from, but is not limited to, and is two-(1-octyloxy-2; 2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 123) etc.This hard coating composition may further include the Photoepolymerizationinitiater initiater of about 0.01wt% to about 1wt%.
This hard coating composition can further comprise other additive as required, like levelling agent, UV-absorbent, surfactant etc.
Preferably, the viscosity of this hard coating composition under 25 ℃ is about 1 to 300cps.In this range of viscosities, this hard coating composition demonstrates good flowability, thereby has improved the productivity ratio that forms hard conating.In one embodiment, the viscosity of said composition is about 10 to 200cps.In another embodiment, the viscosity of said composition is about 50 to 150cps.
According to the hard coating composition of the invention described above embodiment, not only can form hard conating, and give the excellent antifouling property of this hard conating, resistance to impact, resistance to marring etc. with good productivity ratio.
Composite wafer
In the accompanying drawings, for the sake of clarity amplified the size of each device, layer, film and thin slice, each device can further comprise the various additional devices of not describing in the specification.Should be appreciated that when mention certain layer, film or element another layer, film or thin slice " on " time, it can be directly on other layer, film or thin slice, perhaps other layer, film or thin slice also may reside between them.
Fig. 1 is a flow chart of making the method for crooked composite wafer according to embodiment of the present invention.
This method comprises and a) prepares flat compound foil that it comprises decorating film and is formed on the plastic tab layer on this decorating film one side; The hard coating composition that b) will comprise the fluorate acrylic acid ester compounds is deposited on this plastic tab layer; C) through form the hard conating of precuring with this hard coating composition of UV light irradiation; The flat compound foil that d) will have a hard conating of precuring is molded as the have curved surface net shape on (surface); And e) forms the main hard conating that solidifies through hard conating with this precuring of UV light irradiation.
The step of this method will be described below in more detail.
Fig. 2 is a flow chart of making the method for crooked composite wafer according to embodiment of the present invention.This method will be described with reference to figure 2.
Step a) is the process of the flat compound foil 100 of preparation, and this flat compound foil comprises the plastic tab layer 20 on decorating film 10 and the side that is formed on this decorating film 10.
In this step, can utilize laminating roll that plastic tab layer 20 is combined with a side of decorating film 10, thereby prepare flat compound foil 100.This flat compound foil certainly utilizes other method preparation.
Here, thus printed layers 14 is formed on the substrate layer 13 and forms decorating film 10.This process will describe in detail with reference to figure 3.
Step b) is that the hard coating composition that comprises the fluorate acrylic acid ester compounds 30 is deposited on the process on the plastic tab layer 20.
Can be through dip-coating, flow coat, spraying, roller coat, spin coating, intaglio plate coating etc., but be not limited to this, hard coating composition 30 is deposited on the plastic tab layer 20.
In one embodiment, with this hard coating composition be deposited on this plastic tab layer to thickness be about more than 1 to less than about 12.In another embodiment, can this hard coating composition be deposited on this plastic tab layer to thickness about 3 to 10.In interchangeable embodiment, can with this hard coating composition be deposited on this plastic tab layer to thickness be about 3.5 to 7.5.
In one embodiment, before deposition hard coating composition 30, this method further comprises cleans and with UV light irradiated plastics lamella 20, thereby removes remaining oily components and foreign matter.
Step c) is through form the process of the hard conating 40 of precuring with this hard coating composition 30 of UV light irradiation.
In step b), the hard coating composition 30 that is deposited on the plastic tab layer 20 is implemented first solidification process, i.e. precuring, and in following step e), this hard coating composition is implemented the regelate process, promptly main curing.
Through utilizing the UV lamp,, implement solidification process with this hard coating composition of UV light irradiation in the expectation wave-length coverage like high-pressure sodium lamp or metal halide lamp.In step c), this UV light can be according to about 200 to 300mJ/cm
2UV dosage irradiation.
If UV dosage is less than about 200mJ/cm
2, because the hard conating 40 of precuring and the adhesive force between the plastic tab layer 20 are not enough, thereby the hard conating of this precuring may separate with this plastic tab layer in regelate is handled.If UV dosage surpasses about 300mJ/cm
2, then precuring hard conating 40 is caused deterioration in elongation and causes precuring hard conating 40 in secondary (curing) process, to form crackle by over-cured.
At this paper, term " precuring " is meant the first interim solidification process of implementing before main curing the in step e).The case hardness of hard conating 40 of precuring that stands the precuring process is for about 1B1H, and percentage elongation is about more than 300%.
In another embodiment; Before this hard coating composition 30 of precuring; This method can further comprise through heating the plastic tab layer that deposits hard coating composition 30 on it in about 40 to 80 ℃ of following dryings or UV, remove the organic solvent that remains in the hard coating composition 30.
In one embodiment, hard conating (thickness) preferable range that is formed by the hard coating composition of drying is about 1 to 10.When the thickness of this hard conating departed from this scope, molding processability ability and glossiness can deteriorations.More preferably, hard conating (thickness) scope that is formed by the hard coating composition of drying is about 3 to 7.5.In another embodiment, this hard conating thickness is about 3.5 to 7.
Step d) is the process that the flat compound foil 100 with precuring hard conating 40 is molded as the net shape with curved surface.
The flat compound foil 100 that in one embodiment, will have a precuring hard conating 40 is molded as the process of the net shape with curved surface and implements through vacuum mo(u)lding.Vacuum mo(u)lding is implemented through following steps: aperture or narrow groove through being formed in the mould are bled to the space that is surrounded by thin slice and die surface, and make this chip sorption to this mould, thereby form the goods of expectation.The article shape that obtains through vacuum mo(u)lding depends on the shape of this mould.Usually, the article shape that obtains through vacuum mo(u)lding is not a flat shape, but it is round-shaped to have certain three-dimensional, that is, and and curved shape.In this embodiment, have the curved shape that the flat compound foil 100 of precuring hard conating 40 forms and be shown to have curved surface in step d), but should be noted that the present invention is not limited to this.
Step e) is through forming main process of solidifying hard conating 50 with UV light irradiation precuring hard conating 40.
As stated, the hard coating composition 30 that is deposited on the plastic tab layer 20 is carried out precuring, according to the regelate process in the step e) it is led curing then according to the first solidification process among the step c.
Through utilizing the UV lamp,, implement solidification process with this hard coating composition of UV light irradiation in the expectation wave-length coverage like high-pressure sodium lamp or metal halide lamp.In step e), this UV light can be with about 500mJ/cm
2Above UV dosage irradiation.In one embodiment, this UV light can be with about 600 to about 1500mJ/cm
2UV dosage irradiation.
If this UV dosage is less than about 500mJ/cm
2, then being somebody's turn to do main case hardness or the adhesive force that solidifies hard conating will be because of UV underdosage deterioration.
Term " main curing " is meant the secondary master solidification process of implementing after the first precuring process in step c).The case hardness of the main cured layer 50 that forms through secondary master solidification process is more than the 4H.
When preparing crooked composite wafer with this method, this bending composite wafer is compared with the composite wafer that makes through existing spraying or dipping process, can have than low ratio of defects, than the coating surface of high-flatness, reaches better high glaze quality.
Particularly, the flatness of a certain coating surface generally can be confirmed through glossiness difference.When utilizing 60 degree glossiness testers to measure, the surface gloss of the composite wafer through existing spraying or the preparation of dip-coating process is no more than about 95%.By contrast, surpass through surface gloss according to the composite wafer of the method for this embodiment preparation about 95%, thereby make it can show the high gloss quality.
Fig. 3 illustrates a kind of embodiment according to the method for manufacturing decorating film 10 of the present invention.
At first, be imprinted on the substrate layer 13 through designing like floral pattern with printing ink, thereby printed layers 14 is formed on the substrate layer 13 of preparation according to calendering technology (calender process).This calendering technology can easily be implemented by those of ordinary skills.Then, thus adhesive be deposited on form second adhesive linkage 15 on the printed layers 14.
By means of second hyaline membrane 16 that is arranged on second adhesive linkage 15, utilize the coupling system (not shown) that substrate layer 13, printed layers 14, second adhesive linkage 15 and second hyaline membrane 16 are combined, thereby form single sheet 10a.
In interchangeable embodiment, this method may further include solidification process, wherein thin slice 10a is placed in the curing room about 60 to 80 hours, can combine fully so that guarantee substrate layer 13, printed layers 14, second adhesive linkage 15 and second hyaline membrane 16.
Then, thin slice 10a is preheated suitable temperature, utilize embossing calender 500 that it is carried out burr (raised carving) or dimpled grain (depressed carving) compacting then, thereby on thin slice 10a, form relief pattern.
Simultaneously, thus adhesive be deposited on form first adhesive linkage 12 on first hyaline membrane 11.Then; The thin slice 10b that will have relief pattern is placed on first adhesive linkage 12; Make substrate layer 13 towards first adhesive linkage 12, and utilize coupling system to make first hyaline membrane 11, first adhesive linkage 12 and thin slice 10b with relief pattern combines, thereby form preparatory decorating film 10 (10c).Alternatively, first adhesive linkage 12 can be formed on substrate layer 13 belows, rather than is formed on first hyaline membrane 11.
In interchangeable embodiment; This method further comprises solidification process; The thin slice 10b that guarantees first hyaline membrane 11, first adhesive linkage 12 and have a relief pattern wherein preparatory decorating film 10 (10c) is placed in the curing room about 20 to 30 hours, so that can combine fully.
Then, thus pressure-sensitive adhesive is deposited on second hyaline membrane 16 of preparatory decorating film 10 and forms pressure-sensitive adhesive layer 17.In this case, in order to protect pressure-sensitive adhesive layer 17, can be with mould release membrance (release film) 18 attached on the pressure-sensitive adhesive layer 17.
Fig. 4 to 6 illustrates the embodiment through the crooked composite wafer of the manufacturing approach preparation of above-mentioned composite wafer.
With reference to figure 4, crooked decorative panel comprises decorating film 10, is formed on the plastic tab layer 20 on the decorating film 10 and is formed on the hard conating on the plastic tab layer 20.
Formation printed layers 14 prepares on the substrate layer 13 thereby decorating film 10 is through being imprinted on various patterns with printing ink.
With reference to figure 5, in another embodiment, decorating film 10 may further include the pressure-sensitive adhesive layer 17 on printed layers 14.In this case, plastic tab layer 20 can be formed on the pressure-sensitive adhesive layer 17.Pressure-sensitive adhesive layer 17 is formed on this printed layers through pressure-sensitive adhesive is deposited on the printed layers 14.
Printed layers 14 can form through any printing process.For example, silk-screen or intaglio printing can be advantageously used in and show various patterns and color through printed layers 14 efficiently.
Pressure-sensitive adhesive layer 17 can form through deposition (methyl) acrylic acid or silicone pressure-sensitive adhesive.Here, this pressure-sensitive adhesive can be transparent pressure-sensitive adhesive, thereby makes printed layers 14 high-visible through this pressure-sensitive adhesive layer.
This decorating film can have various sandwich constructions, and is not limited to certain structure.
With reference to figure 6; In interchangeable embodiment; Decorating film comprises first hyaline membrane 11, be formed on first adhesive linkage 12 on first hyaline membrane 11, be attached to first adhesive linkage 12 substrate layer 13, be formed on printed layers 14 on the substrate layer 13, be formed on second adhesive linkage 15 on the printed layers 14, be attached to second hyaline membrane 16 of second adhesive linkage 15 and be formed on the pressure-sensitive adhesive layer 17 on second hyaline membrane 16.
First hyaline membrane 11 and second hyaline membrane 16 can, but be not limited to, by olefin resin such as polyethylene (PE), polypropylene (PP) and PET (PET), acryhic material, or polyvinyl chloride (PVC) forms.
First adhesive linkage 12 and second adhesive linkage 15 form through the adhesive that deposition can make first hyaline membrane 11, second hyaline membrane 16 and substrate layer 13 combine closely each other.This adhesive can easily be selected by those of ordinary skills.
Printed layers 14 generally is formed on the upper surface of substrate layer 13.Replacedly, printed layers 14 can be formed on the lower surface of this substrate layer through back printing (rear-side printing).
For the surperficial illumination of stablizing decorating film 10 also strengthens its interior decorative effects simultaneously, can substrate layer 13, printed layers 14, second adhesive linkage 15 and second hyaline membrane 16 be formed to have relief pattern.
Simultaneously, can mould release membrance 18 be attached to the upper surface of the pressure-sensitive adhesive layer 17 of decorating film 10.Mould release membrance 18 can be protected pressure-sensitive adhesive layer 17, and separates with pressure-sensitive adhesive layer 17 easily, because this mould release membrance is attached to this pressure-sensitive adhesive layer with low adhesive force.When decorating film 10 comprises pressure-sensitive adhesive layer 17 with mould release membrance 18,, then plastic tab layer 20 is attached on the pressure-sensitive adhesive layer 17 of decorating film 10 making decorating film 10 combine with plastic tab layer 20 to remove mould release membrance 18 from pressure-sensitive adhesive layer 17 before.
According to following embodiment and comparative example, the present invention will be more readily understood.These embodiment only are used for illustration purpose, do not limit the scope of the invention, and the scope of the invention is defined by the claims.
Embodiment
Thereby after utilizing screen printer floral pattern to be imprinted on the polyethylene film to form printed layers; (A&G Lab PR-910) is deposited on this printed layers with acrylic acid transparent pressure sensitive adhesive; And the polyester mould release membrance is attached to this acrylic pressure sensitive adhesive layer, thereby preparation decorating film.Remove this mould release membrance from prepared decorating film, make the thick PMMA thin slice of this decorating film and 0.3mm (Saehwa Precision Industries company) thus through laminating roll this decorating film is combined with the PMMA thin slice.Utilize the diacrylate resin of bisphenol-A of the oxirane modification of the fluorate acrylic acid ester compounds (Dainippon Ink Chemicals company) of the about 20wt% of flow coat deposition, the double pentaerythritol methacrylate of about 30wt%, the 1-hydroxy-cyclohexyl phenyl ketone of about 0.5wt%, about 3wt%; Methyl cellosolve with 46.5wt%; With decorate the hard conating that forms hard coating composition on the membrane-bound PMMA thin slice, thereby and make this hard conating through removing organic solvent wherein in 60 ℃ to 75 ℃ the drying machine.The thickness of hard conating under drying regime that is formed by this hard coating composition is 5.Through utilizing high-pressure sodium lamp with 300mJ/cm
2This hard conating of UV dose irradiation, carry out precuring.Then, utilize vacuum mold molding machine (obtaining) to make the goods that comprise curved surface from V.F.Korea company.Through with about 700mJ/cm
2The UV dose irradiation comprise that the precuring hard conating of curved surface leads curing, make final crooked composite wafer.
Comparative example 1
According to embodiment in identical process prepare final crooked composite wafer, the thickness of hard conating under drying regime that is just formed by hard coating composition is 15.
Comparative example 2
According to embodiment in identical process prepare final crooked composite wafer, just through with about 100mJ/cm
2This hard conating of UV dose irradiation carry out precuring.
Comparative example 3
According to embodiment in identical process prepare final crooked composite wafer, just through with about 700mJ/cm
2This hard conating of UV dose irradiation carry out precuring.
The mechanical performance of the crooked composite wafer that makes in embodiment and the comparative example 1 to 3 is utilized method of testing and the testing equipment of listing in the table 1.
Table 1
The result of the crooked composite wafer mechanical performance that makes in embodiment and the comparative example 1 to 3 provides in table 2.
Table 2
As shown in table 2, the case hardness of embodiment is measured as 1H after according to precuring, and after with 200% percentage elongation moulding, does not have crackle, therefore demonstrates excellent molding processability ability.In addition, the glossiness of embodiment is about 96%, and this is higher than existing spraying or dip-coating.
For comparative example 1, recording its case hardness is B, but has crackle to form, and therefore demonstrates low molding processability.The glossiness of comparative example 1 is 86%.These performances are owing to 12 thickness of this hard conating, and this thickness is greater than the thickness of hard conating among the embodiment.
The adhesive force that comparative example 2 demonstrates is littler than embodiment.This is owing to about 100mJ/cm
2The UV dosage irradiation hard conating fact of carrying out precuring.
For comparative example 3, recording its case hardness is 2H, but has crackle to form, and therefore demonstrates low molding processability.This is owing to about 700mJ/cm
2The UV dosage irradiation hard conating fact of carrying out precuring.
Therefore, can find out when the crooked composite wafer of preparation expectation that comparative example 1 and 3 demonstrates the remarkable lower molding processability ability than embodiment, and the adhesive force of comparative example 1 is littler than embodiment.
Though this paper has described some embodiment, should be appreciated that these embodiment only are used for illustration purpose, under the situation that does not depart from the spirit and scope of the invention of liking claim and equivalent qualification thereof enclosed, can make various modifications, change and modification.
Claims (20)
1. hard coating composition comprises: about 5 to 60wt% fluorate acrylic acid ester compounds, (methyl) acrylate monomer of about 5 to 50wt%, about Photoepolymerizationinitiater initiater of 0.1 to 10wt% and about 1 to 35wt% bisphenols resin.
2. hard coating composition according to claim 1 further comprises about light stabilizer of 0.01 to 1wt%.
3. hard coating composition according to claim 1, the viscosity of wherein said hard coating composition under 25 ℃ are about 1 to about 300cps.
4. hard coating composition according to claim 3 further comprises the solvent of about 580wt%.
5. composite wafer comprises:
By the hard conating that constitutes according to each described hard coating composition in the claim 1 to 4; With
Be formed on the plastic tab layer on the side of said hard conating.
6. composite wafer according to claim 5, wherein said hard conating be deposited on the said plastic tab layer to thickness be about more than 1 to less than about 12.
7. composite wafer according to claim 5, wherein said hard conating is about more than 95% based on the glossiness of ASTMD-2457, when 200% percentage elongation molded, do not have crackle, and case hardness is more than the 4H.
8. composite wafer according to claim 5, wherein said plastic tab is formed with decorating film on its opposite side.
9. composite wafer according to claim 8, wherein said composite wafer has the shape that comprises curved surface.
10. composite wafer according to claim 8, wherein said decorating film comprises the print film that is formed on the substrate layer.
11. composite wafer according to claim 10, wherein said decorating film further is included in the pressure-sensitive adhesive layer on the said printed layers.
12. composite wafer according to claim 11; Wherein said decorating film comprises first hyaline membrane, be formed on first adhesive linkage on said first hyaline membrane, be attached to said first adhesive linkage substrate layer, be formed on printed layers on the said substrate layer, be formed on second adhesive linkage on the said printed layers, be attached to second hyaline membrane of said second adhesive linkage and be formed on the pressure-sensitive adhesive layer on said second hyaline membrane.
13. composite wafer according to claim 12, at least one in wherein said substrate layer, said printed layers, said second adhesive linkage and said second hyaline membrane has relief pattern.
14. a method of making composite wafer comprises:
A) prepare flat compound foil, it comprises decorating film and is formed on the plastic tab layer on said decorating film one side;
B) will be deposited on the said plastic tab layer according to each described hard coating composition in the claim 1 to 4;
C) through form the hard conating of precuring with the said hard coating composition of UV light irradiation;
The flat compound foil that d) will have a hard conating of said precuring is molded as the net shape with curved surface; And
E) form the main hard conating that solidifies through hard conating with the said precuring of UV light irradiation.
15. method according to claim 14, wherein in step c), said UV light with about 200 to 300mJ/cm
2UV dosage irradiation.
16. method according to claim 14, the case hardness of the hard conating of wherein said precuring is about 1B to 1H.
17. method according to claim 14, wherein in step e), said UV light is with 500mJ/cm
2Above UV dosage irradiation.
18. method according to claim 14, wherein said main case hardness of solidifying hard conating is more than the 4H.
19. method according to claim 14, wherein said hard coating composition be deposited on the said plastic tab layer to thickness be to less than 12 more than 1.
20. method according to claim 14, wherein said decorating film can form through following steps: thus form second adhesive linkage on the said printed layers forming printed layers on the substrate layer and adhesive is applied to; Second hyaline membrane is arranged on said second adhesive linkage and makes said substrate layer, said printed layers, said second adhesive linkage and thereby said second hyaline membrane combines the preparation single sheet; Utilize embossing calender on said thin slice, to form relief pattern; Thereby adhesive is applied on said first hyaline membrane forms first adhesive linkage; The said thin slice that will have a relief pattern be arranged on said first adhesive linkage in case said substrate level to said first adhesive linkage, thereby and the said thin slice that makes said first hyaline membrane, said first adhesive linkage and be formed with relief pattern on it combine to prepare preparatory decorating film; Thereby and pressure-sensitive adhesive is applied on second hyaline membrane of said preparatory decorating film and forms pressure-sensitive adhesive layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090024809A KR101103409B1 (en) | 2009-03-24 | 2009-03-24 | High-glossy curved surface decoration panel and manufacturing method of the same |
| KR10-2009-0024809 | 2009-03-24 | ||
| PCT/KR2009/007836 WO2010110528A1 (en) | 2009-03-24 | 2009-12-28 | Hard coating composition, multi-layered sheet using the same, and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102365179A true CN102365179A (en) | 2012-02-29 |
Family
ID=42781204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801583480A Pending CN102365179A (en) | 2009-03-24 | 2009-12-28 | Hard coating composition, multi-layered sheet using the same, and preparation method thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2012521476A (en) |
| KR (1) | KR101103409B1 (en) |
| CN (1) | CN102365179A (en) |
| WO (1) | WO2010110528A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103607683A (en) * | 2013-08-30 | 2014-02-26 | 歌尔声学股份有限公司 | Loudspeaker diaphragm and manufacturing method thereof |
| CN111137055A (en) * | 2015-03-23 | 2020-05-12 | 雷恩哈德库兹基金两合公司 | Method for applying foil, application device and printing device |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102001134B1 (en) * | 2012-06-01 | 2019-07-17 | 엘지전자 주식회사 | Door for a refrigerator and method for manufacturing the same, decoration panel, method and apparatus for processing a transparent synthetic resine panel |
| CN102964915B (en) * | 2012-11-23 | 2014-07-09 | 东莞市佳烨化工科技有限公司 | Ultraviolet (UV) screen plastic film printing ink and method for preparing same |
| KR101601563B1 (en) | 2014-12-30 | 2016-03-08 | 현대자동차주식회사 | Surface roughness improved high gloss ABS sheet and process for preparing thereof |
| WO2021140874A1 (en) * | 2020-01-08 | 2021-07-15 | リケンテクノス株式会社 | B-stage coating film, laminate film and three-dimensional molded article, and methods respectively for production thereof |
| KR102289115B1 (en) * | 2021-01-06 | 2021-08-24 | 주식회사 티케이 | High gloss exterior panel with excellent low temperature bending resistance and method of manufacturing the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040156983A1 (en) * | 2002-12-17 | 2004-08-12 | Vision-Ease Lens, Inc. | Rapid, thermally cured, back side MAR resistant and antireflective coating for ophthalmic lenses |
| JP2005284142A (en) * | 2004-03-30 | 2005-10-13 | Tomoegawa Paper Co Ltd | Low-reflection member |
| US20060216524A1 (en) * | 2005-03-23 | 2006-09-28 | 3M Innovative Properties Company | Perfluoropolyether urethane additives having (meth)acryl groups and hard coats |
| US20070275171A1 (en) * | 2006-05-29 | 2007-11-29 | Essilor International Compagnie Generale D'optique | Process for Obtaining a Hard Coated Article Having Anti-Fouling Properties |
| CN101107335A (en) * | 2004-12-30 | 2008-01-16 | 3M创新有限公司 | Articles comprising a fluorochemical surface layer and related methods |
-
2009
- 2009-03-24 KR KR1020090024809A patent/KR101103409B1/en not_active IP Right Cessation
- 2009-12-28 CN CN2009801583480A patent/CN102365179A/en active Pending
- 2009-12-28 JP JP2012501919A patent/JP2012521476A/en active Pending
- 2009-12-28 WO PCT/KR2009/007836 patent/WO2010110528A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040156983A1 (en) * | 2002-12-17 | 2004-08-12 | Vision-Ease Lens, Inc. | Rapid, thermally cured, back side MAR resistant and antireflective coating for ophthalmic lenses |
| JP2005284142A (en) * | 2004-03-30 | 2005-10-13 | Tomoegawa Paper Co Ltd | Low-reflection member |
| CN101107335A (en) * | 2004-12-30 | 2008-01-16 | 3M创新有限公司 | Articles comprising a fluorochemical surface layer and related methods |
| US20060216524A1 (en) * | 2005-03-23 | 2006-09-28 | 3M Innovative Properties Company | Perfluoropolyether urethane additives having (meth)acryl groups and hard coats |
| US20070275171A1 (en) * | 2006-05-29 | 2007-11-29 | Essilor International Compagnie Generale D'optique | Process for Obtaining a Hard Coated Article Having Anti-Fouling Properties |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103607683A (en) * | 2013-08-30 | 2014-02-26 | 歌尔声学股份有限公司 | Loudspeaker diaphragm and manufacturing method thereof |
| CN103607683B (en) * | 2013-08-30 | 2017-12-15 | 歌尔股份有限公司 | A kind of diaphragm of loudspeaker and its manufacture method |
| CN111137055A (en) * | 2015-03-23 | 2020-05-12 | 雷恩哈德库兹基金两合公司 | Method for applying foil, application device and printing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012521476A (en) | 2012-09-13 |
| KR20100106714A (en) | 2010-10-04 |
| KR101103409B1 (en) | 2012-01-05 |
| WO2010110528A1 (en) | 2010-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102365179A (en) | Hard coating composition, multi-layered sheet using the same, and preparation method thereof | |
| EP2786876B1 (en) | Transfer film for in-mold injection showing three-dimensional pattern, and preparation method thereof | |
| KR101045282B1 (en) | Decoration Panel Having a Hard Coating Layer and Method of the Same | |
| CN109719892A (en) | The manufacturing method of mould internal shaping transfer film, its manufacturing method and mould internal shaping body | |
| TWI605957B (en) | Interior film including three-dimentional pattern and method for fabricating the same | |
| JP2010284910A (en) | Hard coat film for decoration, decorative film, and decorative molded product | |
| JP5455730B2 (en) | Decorative hard coat film, decorative film and decorative molded product | |
| CN102470657A (en) | Decoration sheet for injection molding | |
| JP5050034B2 (en) | In-mold injection transfer film | |
| CN101898484A (en) | Decoration sheet and method of manufacturing the same | |
| CN109641436B (en) | Two-stage curable laminate | |
| JP2014213596A (en) | Resin laminate | |
| KR20200144273A (en) | Method for manufacturing back cover of mobile device | |
| TW202000799A (en) | Photocurable coating composition and application thereof | |
| JPWO2014125976A1 (en) | Resin laminate | |
| KR20140094260A (en) | Metalic interior sheet with excellent exterior decoration and method of manufacturing the same | |
| KR20100048512A (en) | Uv curable resin composition and process for producing a substrate having a pattern using the same | |
| KR20150123204A (en) | Metalic interior sheet with excellent exterior decoration and method of manufacturing the same | |
| JP7065633B2 (en) | Resin laminate and resin molded product using it | |
| CN101952353B (en) | Production method for an in-mould, semi-cured transfer film | |
| JP6694317B2 (en) | Laminated body and molded body, and methods for producing the same | |
| JP2014205294A (en) | Resin laminate for thermoforming and method for molding the same | |
| KR102431870B1 (en) | Decoration film for metal plate, decoration method of metal plate and metal decoration plate | |
| KR102655183B1 (en) | Decoration film for metal plate and metal decoration plate comprising the same | |
| US20230241874A1 (en) | Resin sheet for molding and molded article using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CI01 | Publication of corrected invention patent application |
Correction item: Claims, specifications Correct: Correct False: Error Number: 09 Volume: 28 |
|
| ERR | Gazette correction |
Free format text: CORRECT: CLAIMS, SPECIFICATION; FROM: ERROR TO: CORRECT |
|
| CI01 | Publication of corrected invention patent application |
Correction item: Claims, specifications Correct: Correct False: Error Number: 09 Volume: 28 |
|
| CI02 | Correction of invention patent application |
Correction item: Claims, specifications Correct: Correct False: Error Number: 09 Page: Description Volume: 28 |
|
| ERR | Gazette correction |
Free format text: CORRECT: CLAIMS, SPECIFICATION; FROM: ERROR TO: CORRECT |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120229 |